Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
  • C08K13/02—Organic and inorganic ingredients
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/24—Acids; Salts thereof
  • C08K3/26—Carbonates; Bicarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K2003/026—Phosphorus

Definitions

• the present invention relates to halogen-free flame-retardant polyester molding compositions with good flame resistance, in particular in the case of thin-walled molded parts containing red phosphorus, nitrogen-containing compounds and small amounts of hydrotalcite, and the use of these molding compositions for the production of moldings, films or fibers and the moldings, films and fibers themselves.
• Flame retardant polyester molding compounds are of great importance in the electrical / electronics sector and are used, for example, to manufacture carriers for live parts. In addition to good flame retardancy, the components must also have good mechanical and electrical properties, whereby the provision of halogen-free molding compounds, in particular with regard to the flame retardants used, is increasingly required.
• JP-A 06-157880 describes molding compositions made from polyalkylene terephthalate, which are made flame-retardant with melamine cyanurate and organophosphates and show good corrosion behavior in addition to good flue gas properties.
• JP-A 11-140290 discloses flame-retardant polyester molding compositions which, in addition to organophosphates and melamine cyanurate, additionally contain fluorine compounds.
• WO 98/30632 discloses flame-retardant thermoplastic polyesters which contain coated red phosphorus and a phenolic novolak resin.
• WO 99/27016 describes red phosphorus in combination with an additional phosphorus compound and a fluoropolymer for flame-retardant adjustment of mixtures of polybutylene terephthalate and polycarbonate.
• JP-A 11-335531 relates to molding compositions made from polybutylene and polyethylene terephthalate which, in addition to coated red phosphorus, contain triazine and cyanuric acid compounds and a polyolefin and are suitable for applications in the electrical / electronics sector.
• polyester molding compositions in particular polybutylene terephthalate, which are equipped with red phosphorus and melamine cyanurate, can be greatly improved by adding small amounts of a hydrotalcite, especially for thin-walled components and moldings.
• the molding compositions according to the invention also have excellent glow wire resistance.
• the present invention thus relates to molding compositions
• % By weight of a flame retardant containing bl) 16 to 50% by weight, preferably 28.5 to 50% by weight, particularly preferably
• E 0 to 50% by weight, preferably 0.001 to 40% by weight, particularly preferably 0.001 to 25% by weight of further additives,
• Polyesters according to component A) are, on the one hand, polyalkylene terephthalates, i.e. Reaction products from preferably aromatic dicarboxylic acids or their reactive derivatives (e.g. dimethyl esters or anhydrides) and aliphatic, cycloaliphatic or araliphatic diols and mixtures of these reaction products, on the other hand also fully aromatic polyesters, which will be described in more detail later.
• aromatic dicarboxylic acids or their reactive derivatives e.g. dimethyl esters or anhydrides
• aliphatic, cycloaliphatic or araliphatic diols and mixtures of these reaction products on the other hand also fully aromatic polyesters, which will be described in more detail later.
• Polyalkylene terephthalates can be prepared from terephthalic acid (or its reactive derivatives) and aliphatic or cycloaliphatic diols with 2 to 10 carbon atoms by known methods (Kunststoff-Handbuch, Vol. VIII, p. 695 FF, Karl-Hanser-Verlag, Kunststoff 1973) ,
• Preferred polyalkylene terephthalates contain at least 80, preferably 90 mol%, based on the dicarboxylic acid, terephthalic acid residues and at least 80, preferably at least 90 mol%, based on the diol component, 1,3-ethylene glycol and / or propanediol and / or butanediol-1,4-residues.
• the preferred polyalkylene terephthalates can contain up to 20 mol% of residues of other aromatic dicarboxylic acids with 8 to 14 C atoms or aliphatic dicarboxylic acids with 4 to 12 C atoms, such as residues of Phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic, adipic, sebacic acid, azelaic acid, cyclohexanediacetic acid.
• the preferred polyalkylene terephthalates can contain up to 20 mol% of other aliphatic radicals.
• diols with 3 to 12 carbon atoms or cycloaliphatic diols with 6 to 21 carbon atoms e.g. Residues of propanediol-1,3,2-ethylpropanediol-1,3, neopentylglycol, pentanediol-1,5, hexanediol-1,6, cyclohexane-dimethanol-1,4,3-methylpentanediol-2,4,2- Methyl-pentanediol-2,4,2,2,4-trimethylpentanediol-1,3 and -1,6,2-ethylhexanediol-1,3,2-diethylpropanediol-1,3, hexanediol-2,5,1 4-di (ß-hydroxyethoxy) benzene,
• the polyalkylene terephthalates can be prepared by incorporating relatively small amounts of trihydric or tetravalent alcohols or trihydric or tetravalent carboxylic acids, e.g. are described in DE-OS 19 00 270 and US Pat. No. 3,692,744.
• preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and propane and pentaerythritol.
• polyalkylene terephthalates which have been produced solely from terephthalic acid and its reactive derivatives (for example its dialkyl esters) and ethylene glycol and or 1,3-propanediol and / or 1,4-butanediol (polyethylene, polypropylene and polybutylene terephthalate), as well as mixtures of these polyalkylene terephthalates.
• terephthalic acid and its reactive derivatives for example its dialkyl esters
• ethylene glycol and or 1,3-propanediol and / or 1,4-butanediol polyethylene, polypropylene and polybutylene terephthalate
• mixtures of polybutylene and polyethylene terephthalate is particularly preferred.
• Preferred polyalkylene terephthalates are also copolyesters which are prepared from at least two of the abovementioned acid components and / or from at least two of the abovementioned alcohol components; particularly preferred copolyesters are poly (ethylene glycol / butanediol-1,4) terephthalates.
• the polyalkylene terephthalates generally have an intrinsic viscosity of approximately 0.4 to 1.5, preferably 0.5 to 1.3, each measured in phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C.
• aromatic dihydroxy compounds also used can be described by the following formula (I),
• Z represents an alkylene or cycloalkylene group with up to 8 carbon atoms, an arylene group with up to 12 carbon atoms, a carbonyl group, an oxygen or sulfur atom, a sulfonyl group or a chemical bond and m has a value from 0 to 2 ,
• the compounds may bear as a substituent Ci-C ö alkyl or alkoxy groups as well as fluorine, chlorine or bromine to the phenylene respectively.
• dihydroxyphenyl di- (hydroxyphenyl) alkane, di- (hydroxyphenyl) cycloalkane, di- (hydroxyphenyl) sulfide, di- (hydroxyphenyl) ether, di- (hydroxyphenyl) ketone, di- (hydroxyphenyl) sulfoxide, di - (Hydroxyphenyl), ⁇ , ⁇ '-di- (hydroxyphenyl) dialkylbenzene, di- (hydroxyphenyl) sulfone, di- (hydroxybenzoyl) benzene, resorcinol and hydroquinone as well as their nuclear alkylated or nuclear halogenated derivatives.
• 2,2-di- (3 ', 5'-dimethyl-4'-hydroxyphenyl) propane 2,2-di- (4'-hydroxyphenyl) propane, 4,4'-dihydroxydiphenylsulfone, 2,2 -Di (3 ', 5-di-chlorodihydroxyphenyl) propane, l, l-di- (4'-hydroxyphenyl) cyclohexane and 3,4'-di-hydroxybenzophenone.
• any mixtures of these and the polyesters mentioned below can also be used.
• Polyesters are also understood to mean polycarbonates and polyester carbonates.
• Polycarbonates and polyester carbonates are known from the literature or can be prepared by processes known from the literature (for the production of polycarbonates see, for example, Schnell, “Chemistry and Physics of Polycarbonates", Interscience Publishers,
• Aromatic polycarbonates are produced e.g. by reacting diphenols with carbonic acid halides, preferably phosgene and / or with aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid dihalides, according to the phase interface method, if appropriate using chain terminators, for example monophenols and if appropriate using trifunctional or more than trifunctional branching agents, for example triphenols Tetra phenols.
• Diphenols for the preparation of the aromatic polycarbonates and / or aromatic polyester carbonates are preferably those of the formula (II)
• B are each C j -C ⁇ alkyl, preferably methyl or halogen, preferably chlorine and / or bromine,
• R 1 and R 2 can be selected individually for each X 1 , independently of one another hydrogen or C 1 -C 6 -alkyl, preferably hydrogen, methyl or ethyl,
• n is an integer from 4 to 7, preferably 4 or 5, with the proviso that at least one atom X 1 R 1 and R 2 are alkyl at the same time,
• Preferred diphenols are hydroquinone, resocin, dihydroxydiphenols, bis- (hydroxyphenyl) -C j -C 5 -alkanes, bis-ydroxypheny -Cs-Cg-cycloalkanes, bis- (hydroxyphenyl) ether, bis- (hydroxyphenyl) sulfoxides, bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones and ⁇ , bis (hydroxyphenyl) diisopropyl benzenes and their core-brominated and / or core-chlorinated derivatives.
• Particularly preferred diphenols are 4,4'-dihydroxydiphenyl, bisphenol-A, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1- Bis- (4-hydroxyphenyl) -3.3.5-trimethylcyclohexane, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone and their di- and tetrabrominated or chlorinated derivatives such as 2,2-bis (3-chloro- 4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane or 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane.
• 2,2-bis (4-hydroxyphenyl) propane (bisphenol-A) is particularly preferred.
• the diphenols can be used individually or in any mixtures.
• the diphenols are known from the literature or can be obtained by processes known from the literature.
• Chain terminators suitable for the production of the thermoplastic, aromatic polycarbonates are, for example, phenol, p-chlorophenol, p-tert-butylphenol or
• 2,4,6-tribromophenol but also long-chain alkylphenols, such as 4- (1,3-tetramethylbutyl) phenol according to DE-A 2 842 005 or monoalkylphenol or dialkylphenols with a total of 8 to 20 carbon atoms in the alkyl substituents such as 3,5-di-tert-butylphenol, p-iso-octylphenol, p-tert-octylphenol, p-dodecylphenol and 2- (3,5-dimethylheptyl) phenol and 4- (3rd , 5-dimethylheptyl) -phenol.
• alkylphenols such as 4- (1,3-tetramethylbutyl) phenol according to DE-A 2 842 005 or monoalkylphenol or dialkylphenols with a total of 8 to 20 carbon atoms in the alkyl substituents such as 3,5-di-tert-butylphenol, p-iso
• Chain terminators are generally between 0.5 mol% and 10 mol%, based on the molar sum of the diphenols used in each case.
• thermoplastic, aromatic polycarbonates have average weight-average molecular weights (M w , measured, for example, by means of an ultracentrifuge or scattered light measurement) of 10,000 to 200,000, preferably 20,000 to 80,000.
• thermoplastic, aromatic polycarbonates can be branched in a known manner, preferably by incorporating from 0.05 to 2.0 mol%, based on the sum of the diphenols used, of trifunctional or more than trifunctional compounds, for example those with three or more phenolic groups.
• Both homopolycarbonates and copolycarbonates are suitable.
• 1 to 25% by weight, preferably 2.5 to 25% by weight (based on the total amount of diphenols to be used) of polydiorganosiloxanes with hydroxy-aryloxy end groups can also be used to produce copolycarbonates according to the invention. These are known (see, for example, US Pat. No. 3,419,634) or can be prepared by processes known from the literature.
• the production of polydiorganosiloxane-containing copolycarbonates is e.g. B. described in DE-A 3 334 782.
• preferred polycarbonates are the copolycarbonates of bisphenol A with up to 15 mol%, based on the molar sum of diphenols, other than the diphenols mentioned as preferred or particularly preferred, in particular 2.2 -bis (3,5-dibromo-4-hydroxyphenyl) propane.
• Aromatic dicarboxylic acid dihalides for the production of aromatic polyester carbonates are, for example, the diacid dichlorides of isophthalic acid, terephthalic acid, diphenyl ether-4,4'-dicarboxylic acid and naphthalene-2,6-dicarboxylic acid.
• Mixtures of the diacid dichlorides of isophthalic acid and terephthalic acid in a ratio between 1:20 and 20: 1 are particularly preferred.
• a carbonic acid halide preferably phosgene, is additionally used as a bifunctional acid derivative.
• Suitable chain terminators for the production of aromatic polyester nor its Chlorkohlen Textreester and the acid chlorides of aromatic monocarboxylic acids which may optionally be substituted by C ⁇ -C 22 alkyl groups or by halogen atoms, and aliphatic C apart from the already mentioned monophenols 2 -C 22 monocarboxylic acid chlorides consideration.
• the amount of chain terminators is in each case 0.1 to 10 mol%, based on moles of diphenols in the case of the phenolic chain terminators and on moles of dicarboxylic acid dichlorides in the case of monocarboxylic acid chloride chain terminators.
• the aromatic polyester carbonates can also contain aromatic hydroxycarboxylic acids as building blocks.
• the aromatic polyester carbonates can be linear or branched in a known manner (see also DE-A 2 940 024 and DE-A 3 007 934).
• Trifunctional or multifunctional carboxylic acid chlorides such as trimesic acid trichloride, cyanuric acid trichloride, 3,3 '-, 4,4'-benzophenonetetracarboxylic acid tetrachloride, 1,4,5,8-naphthalenetetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride, in amounts of 0.01, for example, can be used as branching agents up to 1.0 mol% (based on the dicarboxylic acid dichlorides used) or tri- or polyfunctional phenols, such as phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene-2,4, 4-dimethyl-2,4- 6-tri- (4-hydroxyphenyl) heptane, 1,3,5-tri- (4-hydroxyphenyl) benzene, 1,1,1-tri- (4-hydroxyphenyl) - ethane
• Acid chloride branching agents can be added together with the acid dichlorides.
• the proportion of carbonate structural units in the thermoplastic, aromatic polyester carbonates can vary as desired.
• the proportion of carbonate groups is preferably up to 100 mol%, in particular up to 80 mol%, particularly preferably up to 50 mol%, based on the sum of ester groups and carbonate groups.
• Both the ester and the carbonate content of the aromatic polyester carbonates can be present in the form of blocks or randomly distributed in the polycondensate.
• the relative solution viscosity ( ⁇ re ⁇ ) of the aromatic polycarbonates and polyester carbonates is in the range from 1.18 to 1.4, preferably from 1.22 to 1.3 (measured on solutions of 0.5 g of polycarbonate or polyester carbonate in 100 ml of methylene chloride solution at 25 ° C).
• thermoplastic, aromatic polycarbonates and polyester carbonates can be used alone or in any mixture with one another.
• polyester block copolymers such as. B. copolyether esters as described in US-A 3,651,014.
• a mixture of red phosphorus bl) and nitrogen compound b2) is used as component B) in an amount of 5 to 30% by weight, preferably 10 to 20% by weight, based on the total molding composition. It was found that particularly good results can be achieved in particular in polybutylene terephthalate with 14 to 20% by weight of a mixture of red phosphorus b1) and nitrogen compound b2).
• Red phosphorus according to component bl is to be understood to mean all colored allotropic forms of phosphorus in finely divided form.
• the average particle sizes of these particles are usually in the range between 0.1 and 100 ⁇ m, preferably 0.2 and 50 ⁇ m.
• the particle size of the phosphor can be adjusted by grinding, in particular by wet grinding with ball mills or bead mills. Both water and organic solvents such as toluene, mineral oil, dimethylformamide, dimethylacetamide and formic acid are suitable as grinding media.
• red phosphorus which has been treated or microencapsulated in a known manner.
• Both inorganic materials such as metal hydroxides or silicates and organic compounds, preferably polymers, such as phenol-formaldehyde resins, urea-melamine-phenol, are used for coating or encapsulating the red phosphorus.
• Formaldehyde resins urea-resorcinol-formaldehyde-hexamethylenetetramine resins, epoxy resins, formaldehyde-silicate resins and mixtures of inorganic and organic coating agents. These mixtures can be applied to the red phosphorus simultaneously or in successive steps. In the present context, the use of red
• Phosphorus which has been treated with organic polymers, has proven particularly effective.
• the polymers used are preferably formaldehyde resins, with resorcinol-urea-formaldehyde resins being particularly preferred.
• Typical examples of commercial red phosphorus types are e.g. Products from Clariant such as Red phosphor SFD, Exolit RP 602, Exolit RP 605 or Exolit RP
• Exolit RP 690 Exolit RP 690
• Exolit RP 694 Exolit RP 695
• the last four products being concentrates of red phosphorus in polymeric carrier materials.
• the nitrogen compound b2) used in addition to red phosphorus can be any nitrogen compound b2 used in addition to red phosphorus.
• Melamine cyanurate is particularly preferred in the context of the present invention. This is understood to mean the reaction product of preferably equimolar amounts of melamine and cyanuric acid, which is usually obtained from aqueous solutions and commercially, for example as Melapur® MC 25 (from DSM Melapur, Heerlen, Holland) or Budit® 315 (from Budenheim, Budenheim, Germany) is available.
• the melamine cyanurate can also be treated with known inorganic and / or organic agents. Usual medium
• Particle sizes of the material are between 0.1 and 25 ⁇ m, with medium ones Particle diameters of 0.1 to 10 ⁇ m, preferably 0.1 to 5 ⁇ m are particularly preferred.
• a hydrotalcite according to component C) means a synthetic or natural mineral of the general formula
• M 2+ is a divalent metal ion, preferably Mg 2+ ,
• M 3+ is a trivalent metal ion, preferably Al 3+ ,
• n is an integer greater than 0, preferably 2,
• the combination of the composition is particularly preferred
• Hydrotalcites are available, for example, under the names Hysafe® 539, Nacid®, Sorbplus® PM or Talcid®.
• the hydrotalcites used can optionally be modified by appropriate chemical treatment.
• the molding composition further contains, as component D), 1 to 50% by weight, preferably 10 to 40% by weight, particularly preferably 10 to 35% by weight, of fillers and reinforcing materials.
• Glass balls, glass fabric, glass mats, carbon fibers, aramid fibers, potassium titanate fibers, natural fibers, amorphous silica, magnesium carbonate, barium sulfate, feldspar, mica, silicates, quartz, talc, kaolin, titanium dioxide, wollastonite, etc. can be added, which can also be surface-treated.
• Preferred reinforcing materials are commercially available glass fibers.
• the glass fibers which generally have a fiber diameter between 8 and 18 ⁇ m, can be added as continuous fibers or as cut or ground glass fibers, the fibers being coated with a suitable sizing system and an adhesion promoter or adhesion promoter system, e.g. can be equipped on a silane basis.
• acicular mineral fillers are understood to be mineral fillers with a pronounced acicular character. Needle-shaped wollastonite is an example.
• the mineral preferably has an L / D (length diameter) ratio of 8: 1 to 35: 1, preferably 8: 1 to 1 1: 1.
• the mineral filler can optionally be surface-treated.
• the molding compositions according to the invention may also contain further additives as component E.
• rubber-elastic polymers (often also referred to as impact modifier, elastomer or rubber) as a further additive can prove to be advantageous in some cases with regard to mechanical property professionals.
• these are copolymers which are preferably composed of at least two of the following monomers: ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile and acrylic or methacrylic acid esters with 1 to 18 ° C. -Atoms in the alcohol component.
• Rubber-elastic polymers such as are described in WO 00/1054 and WO 00/46419 are preferred.
• additives are, for example, agents against heat decomposition, agents against heat crosslinking, agents against damage by ultraviolet
• Fluorine-containing compounds such as polytetrafluoroethylene (e.g. Teflon®) being particularly preferred, containing flame-retardant substances, lubricants and mold release agents, nucleating agents, antistatic agents, stabilizers as well as dyes and pigments.
• fluorine-containing compounds such as polytetrafluoroethylene (e.g. Teflon®) being particularly preferred, containing flame-retardant substances, lubricants and mold release agents, nucleating agents, antistatic agents, stabilizers as well as dyes and pigments.
• additives in the form of organic and inorganic metal compounds can be included.
• These include oxides and sulfides of zinc, the oxides and hydroxides of magnesium, copper oxide, iron oxides, metal carbonates such as calcium or magnesium carbonate, borates, in particular zinc borate, and generally stoichiometric mixtures of metal compounds.
• the individual components are mixed in a twin-screw extruder (ZSK 45 from Haake, 20 cm screw length) at temperatures between 260 and 300 ° C., discharged as a strand, cooled to granulation capacity and granulated. After drying (usually two days at 70 ° C in a vacuum drying cabinet)
• Resorcinol-urea-formaldehyde-hexamethylenetetramine resin was coated
• hydrotalcite (Hysafe® 539, J .; Huber Corp., Havre de Grace, USA)
• the flame resistance of plastics is determined using the UL94V method (see a)
• the UL94V-1 classification requires that the individual afterburning times are not longer than 30 seconds and that the sum of the afterburning times of 10 flame treatments of 5 samples is not greater than 250 seconds. The total afterglow time must not exceed 250 seconds. The other criteria are identical to those mentioned above.
• a classification in the fire class UL94V-2 occurs if there is a burning drip if the other criteria of the UL94V-1 classification are met.
• Another test for the flame resistance of plastics is the glow wire test according to DIN IEC 695-2-1.
• the maximum temperature is determined on 10 test specimens (for example on plates with a geometry of 60 x 60 x 2 mm or 1 mm) with the help of a glowing wire at temperatures between 550 and 960 ° C, at which an afterburn time of 30 seconds is not exceeded and the sample does not drip while burning.
• This test is also of particular interest in the electrical / electronics area, since components in electronic products can reach temperatures that are high enough in the event of a fault or overload parts may ignite in the immediate vicinity. Such a thermal stress is simulated in the glow wire test.

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• 2001
  • 2001-06-27 DE DE10130831A patent/DE10130831A1/de not_active Withdrawn
• 2002
  • 2002-06-14 JP JP2003509024A patent/JP2004530784A/ja active Pending
  • 2002-06-14 EP EP02740718A patent/EP1406965A1/de not_active Withdrawn
  • 2002-06-14 BR BR0210669-8A patent/BR0210669A/pt not_active Application Discontinuation
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